Ruthenium-Catalyzed Hydration of 1-Alkynes to Give Aldehydes: Insight into anti-Markovnikov Regiochemistry
- 5 November 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 123 (48) , 11917-11924
- https://doi.org/10.1021/ja0119292
Abstract
The mechanism of the selective conversion of 1-alkynes to aldehydes by hydration was investigated by isolating organic and organometallic byproducts, deuterium-labeling experiments, and DFT calculations. The D-labeled acetylenic hydrogen of 1-alkyne was found exclusively in the formyl group of the resulting aldehydes. After the reaction, the presence of metal-coordinated CO was confirmed. All of the experimental results strongly suggest the involvement of a metal−acyl intermediate with the original acetylenic hydrogen also bound to the metal center as a hydride, with the next step being release of aldehyde by reductive elimination. Theoretical analyses suggest that the first step of the catalytic cycle is not oxidative addition of acetylene C−H or tautomerization of η2-alkyne to a vinylidene complex, but rather protonation of the coordinated 1-alkyne at the substituted carbon to form a metal−vinyl intermediate. This cationic intermediate then isomerizes to Ru(IV)−hydride−vinylidene via α-hydride migration of the vinyl group to the metal center, followed by attack of the vinylidene α-carbon by OH- to give the metal−hydride−acyl intermediate.This publication has 47 references indexed in Scilit:
- Hydride Is Not a Spectator Ligand in the Formation of Hydrido Vinylidene from Terminal Alkyne and Ruthenium and Osmium Hydrides: Mechanistic DifferencesOrganometallics, 1998
- C−C Bond Formation between Vinylidene and Alkynyl Ligands at Ruthenium(II) Leading to either Enynyl or Dienynyl ComplexesOrganometallics, 1996
- Protonation of trans-[Mo(η2-MeCCH)2(Ph2PCH2CH2PPh2)2]: mechanism of formation of trans-[MoX(CHCHMe)(Ph2PCH2CH2PPh2)2](X = Cl or Br) or trans-[MoF(CCH2Me)(Ph2PCH2CH2PPh2)2]J. Chem. Soc., Dalton Trans., 1995
- Catalytic hydration of alkynes with platinum(II) complexesThe Journal of Organic Chemistry, 1993
- Addition of HX Reagents to Alkenes and AlkynesPublished by Elsevier ,1991
- A convenient synthesis of [Ru(η-C5H5)(PPh3)(CO)Cl] and the cations [Ru(η-C5H5)(PPh3)L(CO)]+[L = CO, PMe3, or P(OPh)3]J. Chem. Soc., Dalton Trans., 1984
- Cleavage of the triple bond in phenylacetylene by monomeric ruthenium(II) and osmium(II) complexes. Formation of stable ruthenium(II) alkyls from terminal alkynesJournal of the American Chemical Society, 1982
- Arene ruthenium(II) complexes formed by dehydrogenation of cyclohexadienes with ruthenium(III) trichlorideJ. Chem. Soc., Dalton Trans., 1974
- Formation and Properties of Some Chlorocarbonyl Complexes of Ruthenium(II) and Ruthenium(III)1Journal of the American Chemical Society, 1966
- CATALYSIS OF THE HYDRATION OF ACETYLENIC COMPOUNDS BY RUTHENIUM(III) CHLORIDEJournal of the American Chemical Society, 1961